CN101093887A - Layered lithium-nickel-based compound oxide powder and its manufacturing method - Google Patents
Layered lithium-nickel-based compound oxide powder and its manufacturing method Download PDFInfo
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Abstract
A layered lithium-nickel-based compound oxide powder for a positive electrode material for a high density lithium secondary cell, capable of providing a lithium secondary cell having a high capacity and excellent in the rate characteristics also, is provided. A layered lithium-nickel-based compound oxide powder for a positive electrode material for a lithium secondary cell, characterized in that the bulk density is at least 2.0 g/cc, the average primary particle size B is from 0.1 to 1 um, the median diameter A of the secondary particles is from 9 to 20 [mu]m, and the ratio A/B of the median diameter A of the secondary particles to the average primary particle size B, is within a range of from 10 to 200.
Description
The application divides an application, the international application no of its original application is PCT/JP2004/006694, the China national application number is 200480000392.6, and the applying date is on May 12nd, 2004, and denomination of invention is " layered lithium-nickel-based compound oxide powder and a manufacture method thereof ".
Technical field
The present invention relates to be used for the layered lithium-nickel-based compound oxide powder of positive electrode material of lithium secondary cell and the secondary lithium batteries positive pole and the lithium secondary battery of manufacture method and this layered lithium-nickel-based compound oxide powder of use thereof.Specifically, the present invention relates to provide secondary lithium batteries positive pole and the lithium secondary battery of the high density lithium secondary battery positive electrode material of the also outstanding lithium secondary battery of capacity height and speed characteristic with layered lithium-nickel-based compound oxide powder and manufacture method and use above-mentioned material.
Background technology
Lithium secondary battery has characteristics such as excellent energy density and output density, and can realize miniaturization and lighting, so rapid growth has been appearred in its demand as the power supply of portable sets such as notebook computer, mobile phone and portable video camera.In addition, lithium secondary battery is also as the power supply of electric car and electrical load adjustment etc. and attract tremendous attention.
Employed positive pole is normally by current-collector be formed on the lip-deep positive electrode active material layer of current-collector and constitute in the lithium secondary battery, and this positive electrode active material layer contains positive active material, electric conducting material and adhesive.As positive active material, the composite oxides of lithium such as complex Li-Mn-oxide, lithium cobalt composite oxide or lithium nickel composite oxide and transition metal are attracted attention because of having high performance battery behavior.Use the lithium secondary battery of this lithium system complex oxide to have to obtain the advantage of high voltage and big power output.
For layered lithium-nickel-based compound oxide powder as positive electrode material of lithium secondary cell, usually toast by will containing the former slip spray drying of lithium raw material, nickel compound and transition metal element compound, and to resulting dried particles and to be prepared.In the past, during by this spray drying manufactured lithium-nickel-based compound oxide powder, the viscosity of former slip is important parameters, considers the blow out performance of former slip from spray nozzle, if the viscosity of former slip is crossed low then is difficult to form spherical particle, nozzle stops up easily if viscosity is too high.Therefore the viscosity of common former slip is set in 200～1000cp.In addition, consider that the gas delivery volume during usually with spray drying is set at excessive with respect to slurry from industrial production and the aspect that prevents spray nozzle clogging.When the former slip that has above-mentioned viscosity in use carries out spray drying, gas delivery volume G (L/min) and the ratio G/S (gas/slurry compares) of slurry quantity delivered S (g/min) are set at more than or equal to 5, so that gas is excessive.
But shown in the comparative example 1 of back, the bulk density of the lithium-nickel-based compound oxide powder that obtains under the excessive spray drying condition of such gas reaches 1.77g/cc at most, and can't improve the packed density of positive electrode active material layer.Therefore, need further raising as the bulk density of the positive electrode of lithium secondary battery.
Before baking,, can seek to improve the bulk density of lithium-nickel-based compound oxide powder by in the dried particles that obtains by spray drying, adding sintering aid.But, in this case, owing to promoted growing up of primary particle, so when using such lithium-nickel-based compound oxide powder, have the inadequate problems of battery performance such as speed characteristic and output characteristic.
Summary of the invention
So, the purpose of this invention is to provide the layered lithium-nickel-based compound oxide powder that is used for positive electrode material of lithium secondary cell and the secondary lithium batteries positive pole and the lithium secondary battery of manufacture method and this layered lithium-nickel-based compound oxide powder of use thereof, it is suppressing to make the particle diameter of offspring bigger when primary particle is grown up, even excellent speed characteristic and output characteristic also can be provided under such high volume density.
The layered lithium-nickel-based compound oxide powder that is used for positive electrode material of lithium secondary cell of the present invention is the positive electrode material of lithium secondary cell layered lithium-nickel-based compound oxide powder by following formula (1) expression, it forms offspring by primary particles aggregate and forms, it is characterized in that, its bulk density is more than or equal to 2.0g/cc, the average grain diameter B of primary particle is 0.1～1 μ m, the median particle diameter A of offspring is 9～20 μ m, and the median particle diameter A of offspring and the ratio A/B of the average grain diameter B of primary particle are 10～200.
Li
1+xNi
1-y-z-pMn
yCo
zM
pO
2 (1)
Wherein, 0≤x≤0.20,0.1≤y≤0.5,0.05≤z≤0.5,0≤p≤0.2,0.2≤y+z+p≤0.8; M is at least a kind of element selecting from the group of being made up of Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Nb and Zr.
Promptly, the inventor etc. are through conscientious careful research, found that, condition during by the control spray drying, can suppress growing up and making the particle diameter of offspring bigger of primary particle particle diameter, can obtain to have bigger bulk density and the speed characteristic of excellence and the layered lithium-nickel-based compound oxide powder of output characteristic, thereby finish the present invention.
Lithium-nickel-based compound oxide powder of the present invention has bigger bulk density, and the offspring particle diameter is bigger because the primary particle particle diameter is less, so also have battery performances such as excellent speed characteristic and output characteristic.
What particularly the result of embodiment as described later showed is such, and not only first charge-discharge characteristic excellence can be provided according to the present invention, and the also excellent secondary cell of high-rate discharge characteristic.Discharge capacity when described high-rate discharge characteristic is heavy-current discharge is the characteristic different with first discharge.According to the present invention, even more than or equal to 10mA/cm
2Heavy-current discharge the time, also can obtain bigger discharge capacity.
In addition, in the present invention, the particle diameter B of the average primary particle of layered lithium-nickel-based compound oxide powder is that the value of the average grain diameter of primary particle is to amplify the result who observes ESEM (SEM) determining image with 30000 times.In addition, the value of the median particle diameter A of offspring is to be the result who measured in 1.24 o'clock in refractive index by known laser diffraction/diffuse transmission type particle size distribution analyzer.In the present invention, the decentralized medium of the sodium hexametaphosphate solution that adopts 0.1 weight % when measuring, and after ultrasonic wave disperses 5 minutes, measure.In addition, bulk density is with pack into powder packed density (tap density) after the glass graduated cylinder jolt ramming 200 times of 10ml of the layered lithium-nickel-based compound oxide powder of about 10g.
The BET specific area of preferred layered lithium-nickel-based compound oxide of the present invention is 0.5～1m
2/ g.
The manufacture method that the present invention is used for the layered lithium-nickel-based compound oxide powder of positive electrode material of lithium secondary cell comprises, nickel compound will be dispersed with in the liquid medium, after partly replacing the slurry spray drying of metallic element compound of nickel, mix with lithium compound, and mixture toasted the layered lithium-nickel-based compound oxide powder that is used for positive electrode material of lithium secondary cell with manufacturing, it is characterized in that, during spray drying, if slurry viscosity is V (cp), the slurry quantity delivered is S (g/min), gas delivery volume is G (L/min), and satisfied 0.4≤G/S≤4 and slurry viscosity V and gas/slurry satisfy than the relation of G/S under the condition of G/S≤0.0012V and carry out spray drying than G/S at gas/slurry.
Promptly, under the common in the conventional method spray drying condition that adopts, want the offspring particle diameter of the lithium-nickel-based compound oxide powder that will obtain to resemble and make under the bigger situation of 9～20 μ m the present invention, the essential sintering aid that adds perhaps improves baking temperature and toasts.The result has also promoted growing up of primary particle, and it is big that the primary particle particle diameter becomes easily, and it is in the degree of 1～5 μ m.Therefore, battery performance such as speed and output characteristic is tending towards descending.In addition, even resemble particle diameter to the 0.1～1 μ m that reduces primary particle the present invention, setting lower baking temperature also is essential to suppress growing up of primary particle.Sintering between result's offspring also has been subjected to inhibition, so the particle diameter of offspring in the degree of 4～7 μ m, and is difficult to make it bigger than this.
In contrast, in the present invention, by making gas/slurry than the common-sense condition that is lower than in the conventional spray drying process, and by making the relation that is maintained fixed between slurry viscosity, slurry quantity delivered, the gas delivery volume, can suppress growing up and making the particle diameter of offspring bigger of primary particle particle diameter, obtain bigger bulk density.
In the present invention, can use known BM type viscosimeter that slurry is carried out viscosimetric analysis.BM type viscosimeter is to adopt the mode of the metallic rotator rotation that makes regulation in room temperature environment to carry out method for measuring.When rotor is being in when rotating under the state that is immersed in the slurry, the resistance (twisting resistance) that bears according to its rotating shaft calculates the viscosity of slurry.Room temperature environment is meant common laboratory environment, and promptly temperature is that 10～35 ℃, relative humidity are 20～80%RH.
The layered lithium-nickel-based compound oxide powder that is used for positive electrode material of lithium secondary cell of the present invention also can be made the method that is used for the layered lithium-nickel-based compound oxide powder of positive electrode material of lithium secondary cell of the present invention by such being used to and make.
The feature of secondary lithium batteries positive pole of the present invention is, has positive electrode active material layer on current-collector, and described positive electrode active material layer contains layered lithium-nickel-based compound oxide powder and the adhesive that is used for positive electrode material of lithium secondary cell of the present invention.
In addition, lithium secondary battery of the present invention is the lithium secondary battery that has the negative pole that can absorb-discharge lithium, the nonaqueous electrolyte that contains lithium salts and can absorb-discharge the positive pole of lithium, it is characterized in that the described anodal secondary lithium batteries positive pole of the present invention that adopts.
Description of drawings
Gas/slurry when Fig. 1 is the expression spray drying is than the curve chart of the relation of G/S and slurry viscosity V (cp).
Embodiment
Below, embodiments of the present invention are elaborated.
At first, describe with regard to the layered lithium-nickel-based compound oxide powder that is used for positive electrode material of lithium secondary cell of the present invention.
The layered lithium-nickel-based compound oxide powder that is used for positive electrode material of lithium secondary cell of the present invention is that primary particles aggregate forms the resulting layered lithium-nickel-based compound oxide powder of offspring, its bulk density is more than or equal to 2.0g/cc, the average grain diameter B of primary particle is 0.1～1 μ m, the median particle diameter A of offspring is 9～20 μ m, and the ratio A/B of the median particle diameter A of offspring and primary particle average grain diameter B is 10～200.
The bulk density of layered lithium-nickel-based compound oxide powder of the present invention can meet the requirement to large volume density, for example more than or equal to 2.0g/cc.Especially can realize more than or equal to 2.2g/cc.Though its upper limit is high more good more, be generally the degree of 3g/cc.
In addition, if the average grain diameter B of the primary particle of layered lithium-nickel-based compound oxide powder of the present invention is lower than above-mentioned lower limit, just might produce the problems such as invertibity variation that discharge and recharge because of crystallization is insufficient.In addition, if greater than the upper limit then be difficult to form spherical offspring, the powder fillibility is caused harmful effect, the possibility that battery performances such as speed characteristic and output characteristic are descended becomes big, so be not preferred.So the average grain diameter B of primary particle should be more than or equal to 0.1 μ m, be preferably greater than and equal 0.2 μ m, and should be smaller or equal to 1 μ m, preferably smaller or equal to 0.6 μ m.The particle diameter B of the primary particle of stipulating among the present invention is meant the particle diameter of the primary particle in the layered lithium-nickel-based compound oxide powder that obtains after the baking.
In addition, the median particle diameter A of the offspring of layered lithium-nickel-based compound oxide powder of the present invention is lower than above-mentioned in limited time following, might can't obtain the goods with large volume density given to this invention.In addition, if greater than the upper limit, then battery behavior descends, and perhaps may produce the problem aspect the coating performance when forming positive electrode active material layer, so be not preferred.Therefore, the median particle diameter A of offspring should be more than or equal to 9 μ m, be preferably greater than to equal 10 μ m, and should be smaller or equal to 20 μ m, preferably smaller or equal to 15 μ m.The median particle diameter A of the offspring of the present invention's regulation is meant the median particle diameter A of offspring in the resulting layered lithium-nickel-based compound oxide powder in baking back.
In addition, the ratio A/B of the median particle diameter A of offspring and the average grain diameter B of primary particle represents the trend of offspring size and primary particle size in the positive electrode active material powder, and this A/B 10～200 means that the poised state of battery behaviors such as powder characteristics such as bulk density and speed is good.If this A/B is lower than above-mentioned lower limit, then be difficult to form spherical offspring, so the fillibility of powder descends easily, and in limited time the fillibility of primary particle that is used to form offspring is too high greater than last, so battery behavior descends easily.Therefore, A/B should be more than or equal to 10, are preferably greater than to equal 15, more preferably greater than equaling 30, and should be smaller or equal to 200, preferably smaller or equal to 150, are more preferably less than and equal 100.
For lithium-nickel-based compound oxide of the present invention, the effect of lithium nickel manganese cobalt composite oxide is remarkable, the compound of particularly following formula (1) expression.
Li
1+xNi
1-y-z-pMn
yCo
zMpO
2 (1)
Wherein, 0≤x≤0.20,0.1≤y≤0.5,0.05≤z≤0.5,0≤p≤0.2,0.2≤y+z+p≤0.8; M is at least a kind of element selecting from the group of being made up of Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Nb and Zr.
In above-mentioned formula (1), the lower limit of x is usually more than or equal to 0, is preferably greater than to equal 0.01, and more preferably greater than equaling 0.02, the upper limit is usually smaller or equal to 0.20, preferably smaller or equal to 0.15, is more preferably less than and equals 0.10.If x is greater than 0, so that make the ratio of Li be in the scope of a little higher than stoichiometric composition, then battery performance (particularly speed characteristic and output characteristic) is further enhanced, so be preferred.Though its reason is not fully aware of, can do following supposition.Along with the replacement of excessive Li to transition metal site (3b), the chemical valence of Ni change (Ni (II) → Ni (III)), the ratio of Ni (III)/Ni (II) increases (average valence of Ni rises), and the electronic state of crystal changes as a result, conductivity be improved (resistivity reduction).In addition, Ni (II) reduces the randomness that can suppress crystal structure to the replacement amount (occupation rate) of Li site (3a), and it is steady that the diffusion of Li ion also becomes.The value of x is prescribed a time limit less than this time, the product of meeting remained unreacted, and perhaps crystal structure is tending towards unstable, and prescribe a time limit greater than last, be easy to generate heterogeneously, perhaps got too much, might cause adopting the decreased performance of the lithium secondary battery of these oxide powders by the Li site quantitative change that transition metal replaced.
In addition, the lower limit of y is usually more than or equal to 0.1, is preferably greater than to equal 0.2, and the upper limit is usually smaller or equal to 0.5, preferably smaller or equal to 0.4.Y is lower than this time in limited time, and then the advantage when oxide powder is used for battery is difficult to realize, and surpasses last prescribing a time limit, and will be difficult to synthetic single phase.
In addition, the lower limit of z is usually more than or equal to 0.05, is preferably greater than to equal 0.1, and more preferably greater than equaling 0.2, the upper limit is usually smaller or equal to 0.5, preferably smaller or equal to 0.4.Z is lower than this time in limited time, the synthetic difficulty that might become, and greater than last in limited time, might be disadvantageous aspect the fail safe of battery and the cost.
In addition, the lower limit of p is usually more than or equal to 0, is preferably greater than to equal 0.01, and the upper limit is usually smaller or equal to 0.2, preferably smaller or equal to 0.1.P greater than on this in limited time, the capacity with oxide powder during as the electrode of battery descends, or is difficult to obtain powder properties of the present invention.
In addition, the lower limit of y+z+p is usually more than or equal to 0.2, is preferably greater than to equal 0.3, and the upper limit is usually smaller or equal to 0.8, preferably smaller or equal to 0.7.Y+z+p is lower than this time in limited time, the synthetic difficulty that becomes, and perhaps chemical stability is easy to descend, and oxide powder worsens because of absorbing carbon dioxide etc. when for example preserving, and greater than prescribing a time limit this on, the capacity when oxide powder is used for battery may significantly descend.
Substituted element M is at least a kind of element selecting from the group of being made up of Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Nb and Zr.Especially preferably have the element that can suppress the character that primary particle grows up, from suppressing the angle that primary particle is grown up, M is preferably Al.
The BET specific area of layered lithium-nickel-based compound oxide powder of the present invention is preferably greater than and equals 0.5m
2/ g is preferably greater than especially and equals 0.6m
2/ g, and preferably smaller or equal to 2.0m
2/ g is especially preferably smaller or equal to 1.0m
2/ g.The BET specific area is less than prescribing a time limit under this scope, and battery performance descends easily; During greater than this range limit, be easy to generate problem aspect the coating when forming positive electrode active material layer.
Layered lithium-nickel-based compound oxide powder of the present invention is especially preferably by the spray drying manufactured, and particularly the powder with following shape facility that obtains by spray drying process can obtain higher performance.
That is, the orientation by the observed primary particle that is used to form offspring of section S EM is low is preferred.This shows primary particle crystal random aggregation and forms offspring that offspring does not have the anisotropy of crystal in fact.Therefore, in the offspring, crystal is along with the expansion of lithium ion absorption-release and contraction obtain relaxing, and becomes excellent as the cyclic reversibility of battery behavior.The low orientation of the primary particle by will forming offspring is compared with traditional product with combined by limiting the effect that material of the present invention produces, and can obtain the various battery behaviors that improve with good balance mode, and higher density.
The method that manufacturing the present invention is used for this layered lithium-nickel-based compound oxide powder of positive electrode material of lithium secondary cell is not particularly limited, yet, preferably make the layered lithium-nickel-based compound oxide powder that the present invention is used for positive electrode material of lithium secondary cell according to following method.
Promptly, the method that manufacturing is used for the layered lithium-nickel-based compound oxide powder of positive electrode material of lithium secondary cell comprises: after liquid medium is dispersed with nickel compound, can partly replaces the slurry spray drying of metallic element compound of nickel, mix with lithium compound, the baking mixture, described spray drying is carried out under the following conditions: to establish slurry viscosity and be V (cp), slurry quantity delivered be S (g/min), when gas delivery volume is G (L/min), make gas/slurry than the satisfied 0.4≤G/S of G/S≤4, and slurry viscosity V and gas/slurry satisfy G/S≤0.0012V than the relation of G/S.
If it is above-mentioned in limited time following that gas/slurry is lower than than G/S, then drying property decline and nozzle stop up easily; And if in limited time must use highly viscous slurry greater than last to obtain particle properties given to this invention, the result causes nozzle to stop up easily.So gas/slurry should be more than or equal to 0.4 than G/S, be preferably greater than and equal 0.5, and smaller or equal to 4, preferably smaller or equal to 2, be more preferably less than and equal 1.5.
When slurry viscosity V (cp) and gas/slurry satisfy G/S＞0.0012V than the relation of G/S, because relative slurry viscosity, gas/slurry is than too high, so can not obtain effect of the present invention, promptly by gas/slurry is lower than what set, suppress growing up of primary particle particle diameter and make the particle diameter of offspring bigger, and obtain big bulk density.So, set G/S≤0.0012V.
Like this, in the method for the present invention, than the satisfied 0.4≤G/S of G/S≤4, slurry viscosity V (cp) and gas/slurry satisfy than the relation of G/S under the condition of G/S≤0.0012V and carry out spray drying at gas/slurry.In the curve chart shown in Figure 1, transverse axis is V, and the longitudinal axis is G/S, and hatched example areas is represented described spray-dired condition.In the lower right area of this hatched example areas, promptly slurry viscosity V is big more, gas/slurry is more littler than G/S, the α among the relational expression G/S=α V is more little, and then the median particle diameter A of the offspring of gained powder is big more, and bulk density is big more simultaneously.
Under spray drying condition of the present invention, consider other conditions, the lower limit of the α among the G/S=α V can not limit without exception, and optionally suitably sets according to accessing the powder that has smaller or equal to the median particle diameter A of the offspring of 20 μ m.From aspects such as operability, preferably this α is 0.0004～0.0010.
In addition, among the present invention, if low excessively for the viscosity V (cp) of spray-dired slurry, just might be difficult to form spherical particle, too high then supply pump might be out of order, and perhaps nozzle stops up easily.So slurry viscosity V (cp) is preferably greater than and equals 350cp, be preferably greater than especially and equal 500cp, and preferably smaller or equal to 3000cp, especially preferably smaller or equal to 1500cp, especially preferably smaller or equal to 1200cp.
Slurry quantity delivered S or gas delivery volume G can not limit according to suitably setting for the viscosity of spray-dired slurry and the characteristic of employed spray-drying installation etc. without exception.Yet the lower limit of slurry quantity delivered S (g/min) is generally more than or equal to 10, is preferably greater than to equal 20, and the upper limit is generally smaller or equal to 45, preferably smaller or equal to 40.If be lower than this lower limit, then might reduce productivity ratio, and surpass last prescribing a time limit, then might be difficult to carry out drying.In addition, the lower limit of gas delivery volume G (L/min) is generally more than or equal to 20, is preferably greater than to equal 25, and the upper limit is generally smaller or equal to 45, preferably smaller or equal to 40.When less than this time in limited time, then drying property descends, and perhaps nozzle stops up easily, if surpass the upper limit, then might be difficult to form offspring.
In the method for the present invention, satisfying above-mentioned gas/slurry than G/S, gas/slurry relational expression, and preferably carrying out spray drying in the scope of above-mentioned slurry viscosity, slurry quantity delivered and gas delivery volume than G/S and slurry viscosity V.Other condition is according to the kind of employed equipment and decision aptly, the following condition of further preferential selection.
That is, the spray drying of slurry usually more than or equal to 50 ℃, be preferably greater than equal 70 ℃, more preferably greater than equaling 120 ℃, usually smaller or equal to 300 ℃, smaller or equal to 250 ℃, be more preferably less than the temperature that equals 200 ℃ and carry out.If this temperature is too high, the granulated pellet that then obtains might mostly be hollow structure, and the packed density of powder is tending towards descending.On the other hand, if this temperature is low excessively, then might produce problems such as powder set obstruction because of the condensate moisture of dust outlet part.
In addition, for the air-flow that flows out from spray nozzle, usually with more than or equal to 100m/sec, be preferably greater than the gas line speed that equals 200m/sec and spray.If it is little that this linear gas velocity is spent, then be difficult to form suitable drop.But because be difficult to obtain very big linear velocity, jet velocity is usually smaller or equal to 1000m/sec.
In addition, during layered lithium-nickel-based compound oxide powder made according to the method for the present invention, be used for preparing the starting compound of slurry, can enumerate Ni (OH) as nickel compound
2, NiO, NiOOH, NiCO
32Ni (OH)
24H
2O, NiC
2O
42H
2O, Ni (NO
3)
26H
2O, NiSO
4, NiSO
46H
2O, aliphatic acid nickel, nickel halogenide etc.Do not produce NO during from baking processing
xAnd SO
xSet out etc. the harmful substance aspect, the nickel compound of preferred wherein nonnitrogenous atom or sulphur atom is as Ni (OH)
2, NiO, NiOOH, NiCO
32Ni (OH)
24H
2O, NiC
2O
42H
2O.In addition, further viewpoint that obtains with lower price from can be used as the raw material of industry and reactive high viewpoint particularly preferably are Ni (OH)
2, NiO, NiOOH.These nickel compounds can independent a kind of use, but also two or more is used in combination.
In addition, as manganese compound, can enumerate Mn
2O
3, MnO
2, Mn
3O
4Deng Mn oxide, MnCO
3, Mn (NO
3)
2, MnSO
4, manganese salt such as manganese acetate, dicarboxylic acids manganese, manganese citrate, aliphatic acid manganese, halide such as oxyhydroxide, manganese chloride etc.In these manganese compounds, preferred MnO
2, Mn
2O
3, Mn
3O
4, because it does not produce NO when baking processing
x, SO
x, CO
2Deng gas, and can be used as the raw material of industry with cheap price acquisition.These manganese compounds can be used alone, and also can two or more be used in combination.
In addition, as cobalt compound, can enumerate Co (OH)
2, CoO, Co
2O
3, Co
3O
4, CoOOH, Co (OCOCH
3)
24H
2O, CoCl
2, Co (NO
3)
26H
2O, Co (SO
4)
27H
2O etc.Wherein, based on not producing NO when the roasting procedure
x, SO
xEtc. the angle of harmful substance, preferred Co (OH)
2, CoO, Co
2O
3, Co
3O
4But obtain and reactive high angle, more preferably Co (OH) based on industrial low price
2These cobalt compounds can be used alone, and also can two or more be used in combination.
In addition, in the above-mentioned formula (1), oxyhydroxide, oxide, hydroxide, the halide of substituted metal can be used in the substituted element source that M represents (following also claim " substituted metal compound "), can use the inorganic acid salts such as carbonate, nitrate, sulfate of substituted metal in addition; Acylates such as monocarboxylate such as acetate, oxalate, dicarboxylate, soap etc.
In addition, as the employed decentralized medium of preparation slurry, can use various organic solvents, aqueous solvent, preferred water.In above-mentioned slurry viscosity scope, the ratio of the relative slurry total weight of the total weight of nickel compound and other starting compounds is more than or equal to 10 weight %, be preferably greater than especially and equal 12.5 weight %, and smaller or equal to 50 weight %, especially preferably smaller or equal to 35 weight %.This part by weight is prescribed a time limit less than the following of above-mentioned scope, and slurry concentration is minimum, and the spherical particle that spray drying produces is little of unnecessary degree, and damaged easily.This part by weight is gone up in limited time greater than above-mentioned scope, and the uniformity of slurry is difficult to keep.
The average grain diameter of solid content is usually smaller or equal to 2 μ m in the slurry, especially preferably smaller or equal to 1 μ m, is more preferably less than and equals 0.5 μ m.When the average grain diameter of solid content was excessive in the slurry, not only the reactivity in roasting procedure descended, and sphericity decline, and final powder packed density is tending towards descending.But, make particle little of surpassing the increase that needed degree can cause pulverizing cost, so the average grain diameter of solid content is usually more than or equal to 0.01 μ m, is preferably greater than and equals 0.05 μ m, more preferably greater than equaling 0.1 μ m.
As the method for solid content average grain diameter in the control slurry, can enumerate following method.By ball mill, jet mill etc. starting compound is carried out dry type in advance and pulverize, stir again etc. and to make it be dispersed in method in the decentralized medium; Make after starting compound is dispersed in the decentralized medium by for example stir waiting, working medium agitating type pulverizer etc. carries out the method for case of wet attrition etc.After especially preferably being dispersed in starting compound in the decentralized medium, use medium agitating type pulverizer etc. for example to carry out the method for case of wet attrition.
Gas as being applied when the slurry spray drying can use air, nitrogen etc., uses air usually.Use preferred pressurization back.
As the lithium compound that mixes mutually with the granulated pellet that obtains by spray drying, can enumerate Li
2CO
3, LiNO
3, LiNO
2, LiOH, LiOHH
2O, LiH, LiF, LiCl, LiBr, LiI, CH
3COOLi, Li
2O, Li
2SO
4, lithium acetate, dicarboxylic acids lithium, lithium citrate, fatty acid lithium, lithium alkylide, lithium halide etc.NO does not appear during based on baking processing
x, SO
xEtc. the viewpoint of harmful substance, the lithium compound of the preferably nonnitrogenous atom of these lithium compounds, sulphur atom, preferred LiOH, LiOHH
2O.These lithium compounds can be used alone, and also can two or more be used in combination.
For the particle diameter of such lithium compound, in order to improve the Combination with the resulting desciccate of spray drying, and in order to improve battery performance, its average grain diameter is usually smaller or equal to 500 μ m, preferably smaller or equal to 100 μ m, be more preferably less than and equal 50 μ m, most preferably smaller or equal to 20 μ m.On the other hand, the too small compound of particle diameter stable low in atmosphere equals 0.1 μ m so average grain diameter usually more than or equal to 0.01 μ m, is preferably greater than, more preferably greater than equaling 0.2 μ m, most preferably more than or equal to 0.5 μ m.
Be not particularly limited for the method that spray-dired particle is mixed with lithium compound, but the preferred industrial employed powder equipment usually that uses.In order to prevent to absorb Atmospheric Carbon Dioxide, the atmosphere of the system of mixing therein is preferably atmosphere of inert gases.
Then the mixed-powder to acquisition like this carries out baking processing.Baking condition depends on that raw material forms, and its tendency is, the too high then primary particle of baking temperature can excessively be grown up, and opposite baking temperature is crossed low then bulk density and diminished, and specific area is excessive.The kind of the lithium compound that uses as raw material and other metallic compounds etc. is depended in the variation of baking temperature, usually more than or equal to 700 ℃, be preferably greater than and equal 725 ℃, more preferably greater than equaling 750 ℃, further be preferably greater than and equal 800 ℃, in addition, usually smaller or equal to 1050 ℃, preferably smaller or equal to 1000 ℃.
Temperature is depended in the variation of stoving time, if in aforesaid temperature range, is at least usually 30 minutes, preferably is at least 5 hours, is more preferably at least 10 hours, in addition, mostly is 50 hours usually most.If stoving time is too short, then be difficult to obtain the lithium-nickel-based compound oxide powder of good crystallinity, stoving time is oversize in addition then is unpractical.If stoving time is oversize, also need after the baking to pulverize, perhaps pulverize the difficulty that becomes, so, be more preferably smaller or equal to 20 hours preferably smaller or equal to 25 hours.
According to the The Nomenclature Composition and Structure of Complexes of the compound of manufacturing, the atmosphere during baking can be oxygen containing gas atmosphere or inert gas atmospheres such as nitrogen, argon such as air.
Below, secondary lithium batteries positive pole of the present invention is described.
In the secondary lithium batteries positive pole of the present invention, be formed with positive electrode active material layer on current-collector, this positive electrode active material layer contains layered lithium-nickel-based compound oxide powder and the adhesive that the present invention is used for positive electrode material of lithium secondary cell.
The common following making of positive electrode active material layer.With positive electrode and adhesive and electric conducting material that uses as required and thickener etc. with dry mixed, make sheet, this tablet contact is bonded on the cathode collector, perhaps with these material dissolves or be distributed to and make pulpous state in the liquid medium, then it is coated on the cathode collector body, and carries out drying.
As the material of cathode collector, can use metal material or material with carbon elements such as carbon cloth, carbon paper such as aluminium, stainless steel, nickel plating metal, titanium, tantalum usually.Wherein, be preferably metal material, be preferably aluminium especially.In addition, when using metal material, its shape can be enumerated metal forming, metallic cylinder, wire coil, metallic plate, metallic film, drawn metal, perforated metal (punching metal), foam metal etc., when using material with carbon element, its shape can be enumerated carbon plate, carbon film, carbon cylinder etc.Wherein, metallic film is because of being used for industrial products at present, so be preferred.In addition, film optionally forms suitable netted.
When using film as cathode collector, its thickness can be selected arbitrarily, but usually more than or equal to 1 μ m, is preferably greater than to equal 3 μ m, more preferably greater than equaling 5 μ m, and usually smaller or equal to 100mm, preferably smaller or equal to 1mm, is more preferably less than and equals 50 μ m.If thinner than above-mentioned scope lower limit, the intensity required as current-collector may be abundant inadequately, if the upper limit than above-mentioned scope is big on the other hand, then might be an impediment to handlability.
Employed adhesive is not particularly limited in the positive electrode active material layer to making, when adopting rubbing method to make positive electrode active material layer, as long as its when making for electrode employed liquid medium be stable material.As object lesson, can enumerate resinae macromolecules such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, cellulose, NC Nitroncellulose; Rubber-like macromolecules such as SBR (styrene butadiene rubbers), NBR (acrylonitrile-butadiene rubber), fluorubber, isoprene rubber, butadiene rubber, ethylene-propylene rubber; Thermoplastic elastomer macromolecules such as SBS and hydride thereof, EPDM (ethylene-propylene-diene terpolymers), styrene-ethylene-butadiene vinyl copolymer, SIS and hydride thereof; Between rule-1, flexible resin macromolecules such as 2-polybutadiene, polyvinyl acetate, ethylene-vinyl acetate copolymer, propylene/alpha-olefins copolymer; Kynoar, polytetrafluoroethylene, fluoridize fluoro containing polymerses such as Kynoar, polytetrafluoroethylene-ethylene copolymer; Or has a polymeric composition etc. of the ionic conductivity of alkali metal ion (particularly lithium ion).In addition, these materials can be used alone, but also two or more is used in combination with arbitrary proportion.
In the positive electrode active material layer, the ratio of adhesive is generally more than or equal to 0.1 weight %, be preferably greater than and equal 1 weight %, more preferably greater than equaling 5 weight %, and usually smaller or equal to 80 weight %, preferably, be more preferably, most preferably smaller or equal to 10 weight % smaller or equal to 40 weight % smaller or equal to 60 weight %.The ratio of adhesive is crossed when hanging down, and can't fully keep positive active material, and anodal mechanical strength deficiency, thereby might make deteriorations such as battery performance such as cycle characteristics, on the other hand, if the ratio of adhesive is too high, then might reduce the capacity and the conductivity of battery.
In positive electrode active material layer, contain the electric conducting material that is useful on raising conductivity usually.Be not particularly limited for its kind,, can enumerate metal materials such as copper, nickel as object lesson; Material with carbon elements such as amorphous carbon such as carbon blacks such as graphite such as native graphite, Delanium (graphite), acetylene black, needle-like coke etc.In addition, these materials can be used alone, but also two or more is used in combination with arbitrary proportion.The ratio of electric conducting material is usually more than or equal to 0.01 weight % in the positive electrode active material layer, be preferably greater than and equal 0.1 weight %, more preferably greater than equaling 1 weight %, and usually smaller or equal to 50 weight %, preferably, be more preferably smaller or equal to 15 weight % smaller or equal to 30 weight %.When the ratio of electric conducting material was too low, it is insufficient that conductivity becomes sometimes, if too high then battery capacity descends sometimes on the contrary.
To being not particularly limited as the liquid medium that is used to form slurry, so long as can will get final product as lithium-nickel-based compound oxide powder, adhesive and the electric conducting material that uses as required of positive electrode and the solvent of thickener dissolving or dispersion, aqueous solvent and organic solvent all can use.Example as aqueous solvent can be enumerated water, alcohol etc., can enumerate N-methyl pyrrolidone (NMP), dimethyl formamide, dimethylacetylamide, methylethylketone, cyclohexanone, methyl acetate, methyl acrylate, diethyl triamine, N as representative examples of organic, N-dimethylamino propylamine, oxirane, oxolane (THF), toluene, acetone, dimethyl ether, dimethylacetylamide, hexamethyl phosphoramide, dimethyl methyl acid amides, benzene, dimethylbenzene, quinoline, pyridine, methyl naphthalene, hexane etc.When particularly using aqueous solvent, except that thickener, add dispersant again, and use latex such as SBR to obtain slurry.In addition, these solvents can be used alone, but also two or more is used in combination with arbitrary proportion.
As the positive electrode in the positive electrode active material layer, the content ratio of layered lithium-nickel-based compound oxide powder of the present invention is usually more than or equal to 10 weight %, be preferably greater than and equal 30 weight %, more preferably greater than equaling 50 weight %, and usually smaller or equal to 99.9 weight %, preferably smaller or equal to 99 weight %.Positive electrode active material layer laminate lithium-nickel-based compound oxide powder ratio is too many, and then positive pole strength has not enough trend, if off-capacity very little then sometimes.
In addition, normally about 10～200 μ m of the thickness of positive electrode active material layer.
In addition, preferably carry out compacting through coating, the positive electrode active material layer that obtains of drying, to improve the packed density of positive active material by roll squeezer etc.
Then, lithium secondary battery of the present invention is described.
Lithium secondary battery of the present invention possesses the invention described above secondary lithium batteries positive pole that can absorb-discharge lithium, the negative pole that can absorb-discharge lithium and with the nonaqueous electrolyte of lithium salts as electrolytic salt.In addition, can also possess the dividing plate that keeps nonaqueous electrolyte between positive pole and the negative pole.Short circuit in order to prevent from effectively to cause with contacting of negative pole because of anodal preferably makes dividing plate be present between the two.
Negative pole forms negative electrode active material layer in the mode identical with positive pole usually and constitutes on anode collector.
As the material of anode collector, can use metal material and material with carbon elements such as carbon cloth, carbon paper such as copper, nickel, stainless steel, nickel-plated steel.Wherein, metal material can be enumerated metal forming, metallic cylinder, wire coil, metallic plate, metallic film etc., and material with carbon element can be enumerated carbon plate, carbon film, carbon cylinder etc.Wherein, metallic film is because of being used for industrial products at present, so be preferred.In addition, film can optionally form suitable netted.When using metallic film as anode collector, its suitable thickness range is identical with the scope of above-mentioned cathode collector.
Contain negative electrode active material in the structure of negative electrode active material layer.Negative electrode active material be so long as can absorb-discharge the material of lithium ion and get final product on the electrochemistry, its kind etc. is not had other restriction, and from the high security aspect, use can absorb-discharge the material with carbon element of lithium usually.
As material with carbon element, be not particularly limited for its kind, can enumerate graphite such as Delanium, native graphite; With the thermal decomposition product of organic substance under various thermal cracking conditions.As organic thermal decomposition product, can enumerate coal is that coke, oil are that coke, coal are that Carbonization of Pitch thing, oil are the carbide of Carbonization of Pitch thing or carbide, needle-like coke, pitch coke, phenolic resins or the avicel cellulose etc. of these pitch after oxidation processes etc., perhaps with the graphited material with carbon element of these material parts, furnace black, acetylene black, pitch-based carbon fiber etc.Wherein, be preferably graphite.Especially preferably mainly use the graphite material that contains pitch in various surface-treated Delaniums, refined natural graphite or these graphite etc., these graphite are made the easy graphitization pitch enforcement high-temperature heat treatment that is obtained by various raw materials.These material with carbon elements can be used alone respectively, but also two or more mixes use.
When using graphite material as negative electrode active material, shake the d value (interfloor distance) of the lattice plane (002 face) that method (JSPS regulation method) records by the X diffraction usually more than or equal to 0.335nm according to, and usually smaller or equal to 0.34nm, preferably smaller or equal to 0.337nm.
In addition, the ash content of coal of graphite material is usually smaller or equal to 1 weight % of graphite material weight, preferably smaller or equal to 0.5 weight %, especially preferably smaller or equal to 0.1 weight %.
In addition, the crystallite size (Lc) of the graphite material that is recorded by the X diffraction according to the method for shaking is usually more than or equal to 30nm, is preferably greater than to equal 50nm, is preferably greater than especially to equal 100nm.
In addition, the median particle diameter of the graphite material that records according to laser diffraction-scattering method is usually more than or equal to 1 μ m, be preferably greater than and equal 3 μ m, further be preferably greater than and equal 5 μ m, be preferably greater than especially and equal 7 μ m, in addition, usually smaller or equal to 100 μ m, preferably smaller or equal to 50 μ m, be more preferably less than and equal 40 μ m, especially preferably smaller or equal to 30 μ m.
In addition, the BET method specific area of graphite material is usually more than or equal to 0.5m
2/ g is preferably greater than and equals 0.7m
2/ g is more preferably greater than equaling 1.0m
2/ g further is preferably greater than and equals 1.5m
2/ g, and, usually smaller or equal to 25.0m
2/ g is preferably smaller or equal to 20.0m
2/ g is more preferably less than and equals 15.0m
2/ g is further preferably smaller or equal to 10.0m
2/ g.
In addition, when using argon laser beam that graphite material is carried out Raman spectrum analysis, at 1580～1620cm
-1The peak P that scope detects
AIntensity I
AWith at 1350～1370cm
-1The peak P that scope detects
BIntensity I
BStrength ratio I
A/ I
BBe preferably 0～0.5.In addition, peak P
AHalf-peak breadth preferably smaller or equal to 26cm
-1, be more preferably less than and equal 25cm
-1In addition, except that above-mentioned various material with carbon element, the other materials that can absorb and discharge lithium also can be used as negative electrode active material and uses.As the object lesson of the negative electrode active material outside the material with carbon element, can enumerate metal oxides such as tin oxide or silica, lithium alloys such as lithium simple substance and lithium-aluminium alloy etc.Material outside these material with carbon elements can use separately respectively, also can two or more be used in combination.Also can be used in combination in addition with above-mentioned material with carbon element.
Negative electrode active material layer can be used the manufacture method identical with positive electrode active material layer usually, by with above-mentioned negative electrode active material, adhesive and optionally electric conducting material and thickener formed slurry in liquid medium be coated on the anode collector, and carry out drying and make.Liquid medium, adhesive, thickener and electric conducting material etc. as forming slurry can use with above-mentioned those to be used for the identical material of material of positive electrode active material layer.
As electrolyte, can use for example known organic electrolyte, polymer solid electrolyte, gel-like electrolyte, inorganic solid electrolyte etc., wherein preferred organic electrolyte.Organic electrolyte prepares by solute (electrolyte) is dissolved in the organic solvent.
, the kind of organic solvent is not particularly limited herein, for example can uses carbonates, ethers, ketone, sulfolane compounds, lactone, nitrile, chlorinated hydrocarbon, ethers, amine, ester class, amide-type, phosphate compounds etc.As representational example, can enumerate dimethyl carbonate, diethyl carbonate, propylene carbonate, ethylene carbonate, vinylene carbonate, oxolane, the 2-methyltetrahydrofuran, 1, the 4-diox, 4-methyl-2 pentanone, 1, the 2-dimethoxy-ethane, 1,2-diethoxy ethane, γ-Ding lactones, 1, the 3-dioxolanes, the 4-methyl isophthalic acid, the 3-dioxolanes, ether, sulfolane, methyl sulfolane, acetonitrile, propionitrile, benzonitrile, butyronitrile, valeronitrile, 1, the 2-dichloroethanes, dimethyl formamide, dimethyl sulfide, trimethyl phosphate, triethyl phosphate etc., these can use separately, but also two or more is used in combination.
In order in above-mentioned organic solvent, to dissolve electrolytic salt, preferably in above-mentioned solvent, contain high dielectric constant solvent.Herein, high dielectric constant solvent is meant in the time of 25 ℃ than dielectric constant more than or equal to 20 compound.In the high dielectric constant solvent, the compound after containing hydrogen atom in ethylene carbonate, propylene carbonate and these compounds in the preferred electrolyte and being replaced by other elements such as halogen or alkyl etc.The ratio that high dielectric constant solvent accounts for electrolyte is preferably greater than and equals 20 weight %, more preferably greater than equaling 30 weight %, most preferably more than or equal to 40 weight %.If the content of high dielectric constant solvent than above-mentioned scope after a little while, can not obtain desirable battery behavior sometimes.
Kind to electrolytic salt also is not particularly limited, and can use existing known any solute.As object lesson, can enumerate LiClO
4, LiAsF
6, LiPF
6, LiBF
4, LiB (C
6H
5)
4, LiCl, LiBr, CH
3SO
3Li, CF
3SO
3Li, LiN (SO
2CF
3)
2, LiN (SO
2C
2F
5)
2, LiC (SO
2CF
3)
3, LiN (SO
3CF
3)
2Deng.These electrolytic salts can use any one separately, also can two or more be used in combination with arbitrary proportion.In addition, can also add the CO of arbitrary proportion
2, N
2O, CO or SO
2Deng gas or polysulfide S
x 2-Deng additive, on negative terminal surface, to form the overlay film that lithium ion is is effectively discharged and recharged.
In electrolyte, be generally 0.5mol/L～1.5mol/L as the lithium salts of electrolytic salt.If content is less than 0.5mol/L, perhaps content is greater than 1.5mol/L, and then conductance descends, and battery behavior can worsen sometimes.Lower limit is preferably more than and equals 75mol/L, and the upper limit is preferably smaller or equal to 1.25mol/L.
When using polymer solid electrolyte, its kind is not particularly limited, can use known any crystalline state or amorphous state inorganic matter as solid electrolyte.As the inorganic solid electrolyte of crystalline state, can enumerate for example LiI, Li
3N, Li
1+xJ
xTi
2-x(PO
4)
3(J is Al, Sc, Y or La), Li
0.5-3xRE
0.5+xTiO
3(RE is La, Pr, Nd or Sm) etc.As the amorphous state inorganic solid electrolyte, can enumerate for example 4.9LiI-34.1Li in addition
2O-61B
2O
5, 33.3Li
2O-66.7SiO
2Deng oxide glass etc.These can use any one separately, but also two or more is used in combination with arbitrary proportion.
When using aforesaid organic electrolyte,, dividing plate is placed between positive pole and the negative pole in order to prevent short circuit between the electrode as electrolyte.Material and shape to dividing plate are not particularly limited, and be preferably stable to the organic electrolyte that uses, to protect fluidity outstanding and can prevent the material of short circuit between the electrode really.As preferred example, can enumerate little porous film of containing macromolecular material, sheet, nonwoven fabrics etc.As the object lesson of macromolecular material, can use polyolefin macromolecules such as nylon, cellulose acetate, NC Nitroncellulose, polysulfones, polyacrylonitrile or Kynoar, polypropylene, polyethylene, polybutene.Particularly from viewpoint as the stability on chemistry and electrochemistry of the key factor of dividing plate, the preferred polyolefm family macromolecule, and from self heat insulation viewpoint (this is one of purpose of using the battery by dividing plate), special preferably polyethylene.
When using the dividing plate that is formed by polyethylene, ultra-high molecular weight polyethylene is preferably used in the maintenance aspect of shape under the high temperature, and the lower limit of its molecular weight is preferably 500,000, is more preferably 1,000,000, most preferably is 1,500,000.On the other hand, the upper limit of molecular weight is preferably 5,000,000, is more preferably 4,000,000, most preferably is 3,000,000.If molecular weight too greatly then flowability is low excessively, and the pore volume on the dividing plate easily stops up during heating.
Lithium secondary battery of the present invention can be made by above-mentioned positive pole, negative pole, electrolyte and the dividing plate that uses as required are assembled into suitable shape.In addition, can also use as required as other component parts such as shells.
Shape to lithium secondary battery of the present invention is not particularly limited, and can suitably select from the different shape of common employing according to its purposes.For example, common being shaped as of adopting makes that the inside that spiral helicine column type, pellet electrode and dividing plate be combined into turns up that column type, pellet electrode and the dividing plate of structure is laminated to each other and coin shape of forming etc. with plate electrode and dividing plate.In addition, also be not particularly limited,, can from the whole bag of tricks commonly used, select assemble method aptly according to the reservation shape of battery for the method for assembled battery.
More than the general example of lithium secondary battery of the present invention is illustrated, but lithium secondary battery of the present invention is not limited to above-mentioned example, is being no more than the scope of aim of the present invention, various variations are implemented in addition.
Purposes for lithium secondary battery of the present invention is not particularly limited, and can be used for known various uses.As object lesson, can enumerate notebook computer, the imported PC of pen, mobile PC, E-book reader, mobile phone, portable facsimile printer, portable copier, portable printer, earphone stereo system, video TV, LCD TV, portable type cleaner, portable CD, minidisk, transmitter, electronic notebook, electronic calculator, storage card, portable recorder, broadcast receiver, stand-by power supply, motor, lighting apparatus, toy, game machine, table, photoflash lamp, camera, automobile power source etc.
Embodiment
With embodiment and comparative example the present invention is made more specific description below.
＜be used for the manufacturing of the layered lithium-nickel-based compound oxide powder of positive electrode material of lithium secondary cell 〉
Embodiment 1
With Ni (OH)
2, Mn
3O
4, Co (OH)
2As initiation material, it is carried out weighing, make Ni: Mn: the mol ratio of Co is 0.33: 0.33: 0.33, to wherein adding pure water with the preparation slurry.Stir with circulating medium-stirring wet-type pulverizer (the ダ イ ノ one ミ Le KDL-A type that シ Application マ ス ェ Application one プ ラ イ ゼ ス society produces), pulverizing slurry is 0.15 μ m up to the average grain diameter of solid content.
Then, use two-fluid spray nozzle type spray dryer (the former chemical industry machine in great river (strain) system: the LT-8 type) this slurry (solid content is that 17 weight %, viscosity are 810cp) is carried out spray drying.Employed spray nozzle is an external mix type nozzle, and in the nozzle of concentric circles, the inboard is a slurry outlet, the outside is the gas-pressurized flow export, and nozzle od is 3mm, and the slurry outlet diameter is 2.3mm, the gap of gas-pressurized flow export is 0.2mm, and sectional area is 1.76mm
2Use air as dry gas this moment, and the import volume G of dry gas is 25L/min, and gas line speed is that 237m/sec, slurry import volume S are 39g/min (gas/slurry are than G/S=0.64).In addition, dry inlet temperature is set at 120 ℃.
The interpolation average grain diameter is crushed to the LiOH powder smaller or equal to 20 μ m in the powder of the granulated pellet that obtains by spray drying, and making the mol ratio of Li is 1.05, fully mixes subsequently.Will this mixed-powder of about 13g pack in the aluminum crucible, flow down at the air of 9L/min, in 950 ℃ of bakings 10 hours (heat up or the speed of cooling be 5 ℃/min), obtain having the Li that consists of of layer structure thus
1.05Ni
0.33Mn
0.33Co
0.33O
2The lithium nickel manganese cobalt composite oxide powder.Carry out the evaluation of phase by powder x-ray diffraction.
Will this powder of about 10g pack in the 10ml glass graduated cylinder, the packed density (tap density) of powder is measured in jolt ramming 200 times subsequently, and measurement result is as shown in table 1.In addition, the BET specific area of this powder, the median particle diameter A of offspring (ultrasonic wave disperseed 5 minutes), the ratio of the size of the primary particle by SEM observation, the average grain diameter B of primary particle and A/B is as shown in table 1.
Embodiment 2
Use the solid content average grain diameter to be crushed to the slurry of 0.17 μ m, undertaken in the spray drying by spray dryer, setting the slurry solid content is that 15.5 weight %, viscosity are that 960 cp, dry gas import volume G are that 45L/min, gas line speed are that 426m/sec, slurry import volume S are that 39g/min (gas/slurry is 1.15 than G/S), dry inlet temperature are 90 ℃, it is packed in the square crucible of oxidation aluminum with about 256 g of the mutually mixed powder of LiOH powder through pulverizing, air at 9L/min flowed down, in 950 ℃ of bakings 12 hours.Pulverize subsequently, toasted again 12 hours, operation similarly to Example 1 in addition, the Li that consists of that obtains having layer structure at 950 ℃
1.05Ni
0.33Mn
0.33Co
0.33O
2The lithium nickel manganese cobalt composite oxide powder.
The value of the physical property of this powder of measuring with the method identical with embodiment 1 is as shown in table 1.
Embodiment 3
Use the solid content average grain diameter to be crushed to the slurry of 0.13 μ m, undertaken in the spray drying by spray dryer, setting the slurry solid content is that 16 weight %, viscosity are that 900cp, dry gas import volume G are that 30L/min, gas line speed are that 284m/sec, slurry import volume S are that 35g/min (gas/slurry is 0.86 than G/S), dry inlet temperature are 90 ℃, operation similarly to Example 1 in addition, the Li that consists of that obtains having layer structure
1.05Ni
0.33Mn
0.33Co
0.33O
2The lithium nickel manganese cobalt composite oxide powder.
The value of the physical property of this powder of measuring with the method identical with embodiment 1 is as shown in table 1.
Embodiment 4
Use the solid content average grain diameter to be crushed to the slurry of 0.15 μ m, undertaken in the spray drying by spray dryer, setting the slurry solid content is that 14.5 weight %, viscosity are that 1120cp, dry gas import volume G are that 25L/min, gas line speed are that 237m/sec, slurry import volume S are that 38g/min (gas/slurry is 0.66 than G/S), dry inlet temperature are 120 ℃, the mol ratio of Li is adjusted into 1.10 in the granulated pellet powder that will obtain by spray drying, operation similarly to Example 1 in addition, the Li that consists of that obtains having layer structure
110Ni
0.33Mn
0.33Co
0.33O
2The lithium nickel manganese cobalt composite oxide powder.
The value of the physical property of this powder of measuring with the method identical with embodiment 1 is as shown in table 1.
Comparative example 1
Undertaken in the spray drying by spray dryer, setting the slurry solid content is 17 weight %, viscosity is that 910cp, dry gas import volume G are that 45L/min, gas line speed are that 426m/sec, slurry import volume S are that 10g/min (gas/slurry is 4.50 than G/S), dry inlet temperature are 90 ℃, in addition, operation similarly to Example 1, the Li that consists of that obtains having layer structure
1.05Ni
0.33Mn
0.33Co
0.33O
2The lithium nickel manganese cobalt composite oxide powder.
The value of the physical property of this powder of measuring with the method identical with embodiment 1 is as shown in table 1.
Comparative example 2
Undertaken in the spray drying by spray dryer, to the slurry solid content is that 16 weight %, viscosity are that 900cp, the flat particle diameter of solid content are that the slurry of 0.16 μ m is sprayed, setting dry gas import volume G is that 45L/min, gas line speed are that 426m/sec, slurry import volume S are that 39g/min (gas/slurry is 1.15 than G/S), dry inlet temperature are 120 ℃, the LiOH powder of interpolation through pulverizing, the mol ratio of Li in the granulated pellet powder that this spray drying is obtained is adjusted into 1.05, further adds Bi
2O
3Powder, the mol ratio that makes Bi is 0.005, operation similarly to Example 1 in addition, the Li that consists of that obtains having layer structure
1.05Ni
033Mn
0.33Co
0.33O
2The lithium nickel manganese cobalt composite oxide powder.Carry out the evaluation of phase by powder x-ray diffraction, except that the laminated Li-Ni manganese cobalt composite oxide, also confirm to exist Bi
2O
3Phase.
The value of the physical property of this powder of measuring with the method identical with embodiment 1 is as shown in table 1.
Comparative example 3
Undertaken in the spray drying by spray dryer, setting the slurry solid content is 12 weight %, viscosity is that 250cp, dry gas import volume G are that 30L/min, gas line speed are that 284m/sec, slurry import volume S are that 40g/min (gas/slurry is 0.75 than G/S), dry inlet temperature are 90 ℃, in addition, operation similarly to Example 1, the Li that consists of that obtains having layer structure
1.05Ni
0.33Mn
0.33Co
0.33O
2The lithium nickel manganese cobalt composite oxide powder.
The value of the physical property of this powder of measuring with the method identical with embodiment 1 is as shown in table 1.
Table 1
| Example | The spray drying condition | Bulk density (g/cc) | The median particle diameter A of offspring (μ m) | The particle diameter of primary particle (μ m) | The average grain diameter B of primary particle (μ m) | A/B | BET specific area (m 2/g) | |||
| Slurry viscosity V (cp) | Gas/slurry compares G/S | α value among the G/S=α V | ||||||||
| Embodiment | 1 | 810 | 0.64 | 0.00079 | 2.3 | 11.4 | 0.3～0.6 | 0.5 | 23 | 0.90 |
| 2 | 960 | 1.15 | 0.00120 | 2.1 | 10.0 | 0.5～1.0 | 0.7 | 14 | 0.69 | |
| 3 | 900 | 0.86 | 0.00096 | 2.1 | 9.9 | 0.3～0.6 | 0.5 | 20 | 0.82 | |
| 4 | 1120 | 0.66 | 0.00059 | 2.0 | 10.8 | 0.3～1.0 | 0.5 | 22 | 1.05 | |
| Comparative example | 1 | 910 | 4.5 | 0.00495 | 1.8 | 6.3 | 0.3～0.6 | 0.5 | 13 | 1.04 |
| 2 | 900 | 1.15 | 0.00128 | 2.3 | 11.6 | 1～3 | 1.5 | 8 | 0.37 | |
| 3 | 250 | 0.75 | 0.00300 | 1.9 | 10.2 | 0.3～1 | 0.7 | 15 | 0.90 | |
The making of＜battery and evaluation 〉
Each layered lithium-nickel-based compound oxide powder that use is made by embodiment 1～4 and comparative example 1～3 carries out the making and the evaluation of battery by the following method.
(1) affirmation of Zheng Ji making and first charge/discharge capacity and speed experiment:
Ratio weighing in the polytetrafluorethylepowder powder of the acetylene black of each layered lithium-nickel-based compound oxide powder of making by embodiment 1～4 and comparative example 1～3 of 75 weight %, 20 weight %, 5 weight %, fully mix with mortar, laminate, the stamping machine that this thin slice diameter is 9 mm is gone out.Be adjusted into about 8mg with gross weight this moment.Punching is crimped on the aluminium expanded metal, makes the positive pole that diameter is 9mm.
The positive pole that with the diameter is 9mm as counterelectrode, uses the LiPF that is dissolved with 1mol/L in the solvent of EC (ethylene carbonate): DMC (dimethyl carbonate): EMC (ethylmethyl carbonate)=3: 3: 4 (volume ratio) with the lithium metallic plate as test electrode
6Electrolyte, be that the porous polyethylene film of 25 μ m is assembled button cell as dividing plate with thickness.
For the button cell that obtains, establishing the charging upper voltage limit is 4.3V, and the discharge lower voltage limit is 3.0V, with 0.2mA/cm
2Constant current, carry out discharging and recharging of 2 cycles, then, with 0.5mA/cm
2Constant current charge, respectively with 0.2mA/cm
2, 0.5mA/cm
2, 1mA/cm
2, 3mA/cm
2, 5mA/cm
2, 7mA/cm
2, 9mA/cm
2And 11mA/cm
2Current discharge carries out the test in the 3rd～10 cycle.Measure the period 1 at 0.2mA/cm
2The time first charge/discharge capacity (mAh/g) and the 10th cycle at 11mA/cm
2The time high rate discharge capacity (mAh/g), the result is as shown in table 2.
Table 2
| Example | Initial stage charge/discharge capacity [mAh/g] | High rate discharge capacity [mAh/g] |
| Embodiment 1 | 178/161 | 115 |
| Embodiment 2 | 180/160 | 115 |
| Embodiment 3 | 177/164 | 120 |
| Embodiment 4 | 176/160 | 128 |
| Comparative example 1 | 178/162 | 112 |
| Comparative example 2 | 175/155 | 90 |
| Comparative example 3 | 178/159 | 117 |
The high density lithium positive electrode material for secondary battery of the speed characteristic with high power capacity and excellence can be provided according to the present invention as shown in Table 2.Particularly in embodiment 4, the mol ratio of Li is 1.10, is rich in lithium in the component, thereby high-rate discharge characteristic is excellent especially.
In addition,, do not break away from the intent of the present invention and scope, can carry out various changes though the present invention is had been described in detail with specific execution mode.
In addition, Japan patent of invention spy hope 2003-134695 number (on May 13rd, 2003 filed an application in the Japan special permission Room), Japanese patent of invention spy are willing to that 2003-185175 number (on June 27th, 2003 speciallyyed permit the Room in Japan and files an application), Japanese patent of invention spy are willing to that 2003-377140 number (on November 6th, 2003 speciallyyed permit the Room in Japan and files an application) and the special hope of Japanese patent of invention 2004-026943 number (on February 3rd, 2004 speciallyyed permit the Room in Japan and files an application) are the bases that the application requires priority, and its full content is hereby incorporated by.
Industrial applicibility
According to the present invention, by the layered lithium-nickel-based compound oxide powder as the primary particle particle diameter with less of high density lithium secondary battery positive electrode material, relatively large offspring particle diameter, can provide the lithium secondary battery with high power capacity and excellent speed characteristic.
Claims (8)
1, the layered lithium-nickel-based compound oxide powder that is used for positive electrode material of lithium secondary cell, the composition of described powder is represented with following formula 1, it is that primary particles aggregate forms the resulting layered lithium-nickel-based compound oxide powder of offspring, it is characterized in that, its bulk density is more than or equal to 2.0g/cc, the average grain diameter B of primary particle is 0.1～1 μ m, and the median particle diameter A of offspring is 9～20 μ m, and the median particle diameter A of offspring and the ratio A/B of the average grain diameter B of primary particle are 10～200:Li
1+xNi
1-y-z-pMn
yCo
zM
pO
21
Wherein, 0≤x≤0.20,0.1≤y≤0.5,0.05≤z≤0.5,0≤p≤0.2,0.2≤y+z+p≤0.8; M is at least a kind of element selecting from the group of being made up of Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Nb and Zr.
2, layered lithium-nickel-based compound oxide powder as claimed in claim 1 is characterized in that, its BET specific area is 0.5～1m
2/ g.
3, layered lithium-nickel-based compound oxide powder as claimed in claim 1 or 2 is characterized in that, in the formula 1, y is 0.2～0.4, z is 0.2～0.4, y+z+p is 0.3～0.7.
As each described layered lithium-nickel-based compound oxide powder of claim 1～3, it is characterized in that 4, in the formula 1, x is 0.02～0.10.
5, the method that is used for the layered lithium-nickel-based compound oxide powder of positive electrode material of lithium secondary cell, wherein, nickel compound will be dispersed with in the liquid medium, after partly replacing the slurry spray drying of metallic element compound of nickel, mix with lithium compound, and mixture toasted the layered lithium-nickel-based compound oxide powder that is used for positive electrode material of lithium secondary cell with manufacturing, it is characterized in that, during spray drying, if slurry viscosity is V, unit is cp, the slurry quantity delivered is S, unit is g/min, gas delivery volume is G, when unit is L/min, satisfies than the relation of G/S than the satisfied 0.4≤G/S of G/S≤4 and slurry viscosity V and gas/slurry by gas/slurry under the condition of G/S≤0.0012V and carry out spray drying.
6, the layered lithium-nickel-based compound oxide powder that is used for positive electrode material of lithium secondary cell, described powder are to be made by the manufacture method that is used for the layered lithium-nickel-based compound oxide powder of positive electrode material of lithium secondary cell as claimed in claim 5.
7, the positive pole that is used for lithium secondary battery, it is characterized in that, have positive electrode active material layer on current-collector, described positive electrode active material layer contains just like each described layered lithium-nickel-based compound oxide powder and adhesive that is used for positive electrode material of lithium secondary cell in claim 1～4 or 6.
8, lithium secondary battery, the positive pole that it has the negative pole that can absorb-discharge lithium, the nonaqueous electrolyte that contains lithium salts and can absorb-discharge lithium is characterized in that, uses the positive pole of lithium secondary battery that is used for as claimed in claim 7 as positive pole.
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|---|---|---|---|
| JP2003134695 | 2003-05-13 | ||
| JP2003134695 | 2003-05-13 | ||
| JP2003185175 | 2003-06-27 | ||
| JP2003377140 | 2003-11-06 | ||
| JP2004026943 | 2004-02-03 |
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| CNB2004800003926A Division CN100338801C (en) | 2003-05-13 | 2004-05-12 | Layered lithium nickel composite oxide powder and process for producing the same |
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| CNB2004800003926A Active CN100338801C (en) | 2003-05-13 | 2004-05-12 | Layered lithium nickel composite oxide powder and process for producing the same |
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| CN1698223A (en) | 2005-11-16 |
| CN100338801C (en) | 2007-09-19 |
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